Described herein are the design and development of easily prepared molybdenum pi-complexes of unsaturated oxygen and nitrogen heterocycles (eta-3-pyranyl, eta-3-pyridinyl, and others) of high enantiopurity, which can be richly functionalized then demetalated in a regio- and stereocontrolled fashion. From a common chiral scaffold, demetalation coincident with functionalization will be studied by three core protocols: sequential functionalization allowing attachment of multiple substituents, [5+2] and [5+3] cycloaddition providing access to oxa- and aza-bridged bicyclics, and [4+2] cycloadditions with alkenyl substituted eta-3-pyranyls and eta-3-pyridinyls giving a novel entry to ring-fused heterocycles. In principle, these pi-complexes function as chiral scaffolds of high enantiopurity for the rapid assembly of substituted oxygen and nitrogen heterocyclic systems of known or potential medicinal value. In addition to the obvious exploitation of solution-based protocols, the metal complex "scaffold" approach should be particularly amenable to structure-activity-relationship studies using parallel synthesis technologies. This "enantiomerically-pure scaffold" strategy, if developed to its fullest potential, could hold great promise for rapid SAR studies of substituted oxygen- and nitrogen heterocyclic systems of high enantiopurity.